WO2011036272A2 - Polyester biodégradable - Google Patents

Polyester biodégradable Download PDF

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Publication number
WO2011036272A2
WO2011036272A2 PCT/EP2010/064185 EP2010064185W WO2011036272A2 WO 2011036272 A2 WO2011036272 A2 WO 2011036272A2 EP 2010064185 W EP2010064185 W EP 2010064185W WO 2011036272 A2 WO2011036272 A2 WO 2011036272A2
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WO
WIPO (PCT)
Prior art keywords
biodegradable polyester
acid
polyester according
biodegradable
precursor
Prior art date
Application number
PCT/EP2010/064185
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English (en)
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WO2011036272A3 (fr
Inventor
Catia Bastioli
Luigi Capuzzi
Original Assignee
Novamont S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Novamont S.P.A. filed Critical Novamont S.P.A.
Priority to CN201080042753.9A priority Critical patent/CN102666619B/zh
Priority to CA2773445A priority patent/CA2773445C/fr
Priority to EP10766247.0A priority patent/EP2480582B1/fr
Priority to JP2012530280A priority patent/JP5793497B2/ja
Priority to ES10766247T priority patent/ES2788006T3/es
Priority to US13/497,864 priority patent/US10017597B2/en
Publication of WO2011036272A2 publication Critical patent/WO2011036272A2/fr
Publication of WO2011036272A3 publication Critical patent/WO2011036272A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • the present invention relates to a substantially gel-free and substantially linear biodegradable thermoplastic polyester (BP) comprising units deriving from at least one diacid and at least one diol, obtainable by means of reaction with radical initiators starting from a precursor polyester (PP) provided with an unsaturated chain terminator, said terminator having the formula:
  • T is selected from the group consisting of hydroxylic, carboxylic, amine, amide or ester group and "n" is an integer comprised between 0 and 13.
  • the present invention also relates to a process for obtaining said biodegradable polyester BP.
  • the use of biodegradable polyesters currently available on the market is limited due to various types of drawbacks. For example, there are difficulties related to their rheological properties, which limit their use in the various transformation technologies commonly adopted for conventional plastic materials unless chain extenders of different type are used. However, these chain extenders, such as isocyanates, epoxy acrylates, etc., usually have a much greater impact on the environment than the polyester itself. Another issue linked to the use of such chain extenders is the smell of the final polyesters which is due to the presence of their chemical residues. The latter is particularly critical when using these chain extenders in the production of packaging articles particularly for food packaging applications.
  • JP-2746525 describes a chain extension process with peroxides of hydroxyl terminated aliphatic polyesters, with high molecular weight, extended by a mixture of saturated and unsaturated isocyanates, where the unsaturated isocyanates bear an acrylate group.
  • the acrylic terminal group is inserted in the chain to control the reactivity of the polyesters to the peroxides.
  • polyesters require the use of high amounts of radical initiator.
  • the prepolymer bearing the unsaturated acrylic terminal group is then made to react in a subsequent step with a quantity of peroxides comprised between 0.1 and 5% by weight.
  • said acrylic terminal group must be inserted on a prepolymer having weight average molecular weight (Mw) of over 30,000.
  • JP-2746525 therefore involves a process in three steps and the use of high quantities of organic peroxides, giving rise to polyesters characterized by a number average molecular weight (Mn) around 30,000 and very large molecular weight distribution (MWD).
  • Mn number average molecular weight
  • MWD very large molecular weight distribution
  • WO 2006/053936 discloses a crosslinked thermosetting aliphatic polyester obtained by reacting free radicals with a precursor polyester comprising an hydroxyacid or a diacid and diol, a functionalising agent (which can be a diol or polyfunctional alcohol, or a dicarboxylic acid or polyfunctional carboxylic acid) and possibly other monomers such as ⁇ -capro lactone or unsaturated components like itaconic acid.
  • a functionalising agent which can be a diol or polyfunctional alcohol, or a dicarboxylic acid or polyfunctional carboxylic acid
  • ⁇ -capro lactone or unsaturated components like itaconic acid in order to increase the speed of crosslinking said precursor polyester is end-functionalized with compounds containing double bonds such as methacrylic anhydride.
  • the present invention relates to a substantially gel-free and substantially linear biodegradable thermoplastic polyester BP comprising units deriving from at least one diacid and at least one diol, obtainable by reaction with radical initiators starting from a precursor polyester PP provided with an unsaturated chain terminator, said terminator having the formula:
  • T is selected from the group consisting of hydroxylic, carboxylic, amine, amide or ester group
  • n is an integer comprised between 0 and 13.
  • the biodegradable polyester BP according to the present invention allows the production of starch based compositions showing improved mechanical properties as well as a tear strength superior to that of starch based composition with similar biodegradable polyesters.
  • the present invention also relates to a process for obtaining said biodegradable polyester BP
  • the present invention also relates to the use of chain terminator having formula:
  • T is selected from the group consisting of hydroxylic, carboxylic, amine, amide or ester group, and "n" is an integer comprised between 0 and 13 for the chain extension of polyesters.
  • thermoplastic are meant herein all the polyesters capable of being repeatedly softened and hardened by heating and cooling through a temperature range characteristic for each polyester.
  • thermoplastic polyesters can be shaped by flow into articles, for example by molding or extrusion.
  • Thermoplastic polyesters are therefore different from the curable ones which, by contrast, are polyesters irreversibly hardened by crosslinking of polymer chains. In this state, curable polyesters show a networked structure.
  • substantially gel-free are meant herein all the polyesters showing a gel fraction lower than 5 %(w/w) with respect to the polyester, preferably lower than 3 %.
  • the gel fraction according to the present invention is measured by placing a sample of polyester (X 1 ) in chloroform under reflux for 8 hours, filtering the mixture on a sieve filtering grid of 25-45 ⁇ and weighing the weight of the material that remains on the filtering grid (X 2 ). The gel fraction was determined as the ration of the material so obtained with respect to the weight of the sample (x x ⁇ xlOO.
  • substantially linear are meant herein all the polyesters showing a structure comprising the multiple repetition in linear sequence of repeating units (acids and diols held together by ester linkage) with at most 3% by moles with respect to the quantity of diacids or their derivatives (and hydroxy acids or their derivatives if present) of one or more polyfunctional molecules (i.e. molecules having more than 2 reactively active sites) such as glycerol.
  • the biodegradable polyester BP according to the present invention is characterized in melted state by a Shear Viscosity of 300 to 2,000 preferably between 400 and 1,800 Pas and more preferably 500-1500 Pas.
  • the biodegradable polyester BP When used in applications to produce films the biodegradable polyester BP preferably has a Thermal Stability Constant of less than 2 -10 4 at 180 °C, more preferably less than 1.5 -10 4 at 180 °C and melt strength at 180°C between 0,9 and 3, more preferably between 1 and 2.9 g, still more preferably between 1.1-2.8 g.
  • the Thermal Stability Constant is measured according to the standard ASTM D-3835- Appendix, maintaining the polyester in melted state at a given temperature and measuring, at different times, the Shear Viscosity.
  • the Thermal Stability Constant is expressed as (1 ⁇ ( ⁇ 1/ ⁇ 2))/( ⁇ 2- ⁇ 1), i.e. the ratio between the natural logarithm of ( ⁇ / ⁇ 2) and the difference (t2-tl), where tl and t2 indicate two permanence times of the melt at the test temperature and ⁇ ⁇ and r ⁇ 2 indicate the respective Shear Viscosities.
  • the Melt Strength is measured according the international standard ISO 16790:2005, at
  • the molecular weight M n of the biodegradable polyester BP according to the present invention is preferably between 40,000 and 200,000 and more preferably between 50,000 and
  • the molecular weight Mn can be measured by Gel Permeation Chromatography (GPC). Determination can be conducted with a chromatography system maintained at 40°C, using a set of three columns in series (particle diameter of 5 ⁇ and porosity respectively of 500 A, 1000 A and 10000 A), a refraction index detector, chloroform as eluent (flow 1 ml/min) and using polystyrene as standard of reference.
  • GPC Gel Permeation Chromatography
  • the angular range used is 5-60° (2 ⁇ ) with steps of 0,03° (2 ⁇ ) and acquisition time of 2 seconds per step.
  • the % of crystallinity is calculated as the percentage between the crystalline phase area and the sum of the areas of crystalline and amorphous phases.
  • the Melt Flow Rate (MFR) of the biodegradable polyester BP according to the present invention is preferably between 200 and 1.0 g/10 min, more preferably between 100 and 1.5 g/10 min, even more preferably between 70 and 2 g/10 min (measurement effected at 190°C/2.16 kg according to the standard ASTM D1238-89 "Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer").
  • it preferably has a Melt Flow Rate of less than 10 g/10
  • the precursor polyester PP is able to modulate the action of the radical initiators during the chain extension reactions leading to the formation of substantially linear high molecular weight polymer structures of the biodegradable polyester BP according to the invention. Its high reactivity also allows repeatable and reliable use in chain extension processes using radical initiators, greatly reducing the quantity of radical initiators to be used and at the same time limiting the use of chain extenders of different type as well as the occurence of gels during said processes.
  • unsaturated chain terminator is intended as compounds having the formula:
  • T is selected from the group consisting of hydroxylic, carboxylic, amine, amide or ester group, and "n" is an integer number comprised between 0 and 13.
  • Said unsaturated chain terminators can also be used in mixture.
  • T it is preferably a hydroxylic or carboxylic group.
  • the integer "n” is preferably comprised between 1 and 13, more preferably 3 and 13, still more preferably 8 or 9, omega-undecenoic acid, omega-undecylenic alcohol and mixtures thereof being particularly preferred in order to maximize compatibility with natural polymers.
  • the content of the unsaturated chain terminator is less than or equal to 1 %, preferably between 0.01 - 1 and more preferably between 0.01 - 0.5 % by moles with respect to the moles of repetitive units of the polyester precursor.
  • the precursor polyester is advantageously selected from aliphatic and aliphatic-aromatic biodegradable polyesters.
  • the precursor polyester is an aliphatic-aromatic biodegradable polyester for the production of high thoughness materials.
  • polyesters PP these are composed by at least one aliphatic diacid, at least one aliphatic diol and the unsaturated chain terminator.
  • polyesters PP these have the aromatic part principally composed by at least one aromatic polyfunctional acid and the aliphatic part composed by the unsaturated chain terminator, at least one aliphatic diacid and at least one aliphatic diol.
  • said aliphatic and aliphatic-aromatic polyesters PP can be composed by more than one type of repeating unit (acids and diols held together by ester linkage).
  • said polyesters preferably show a random structure with a randomness index of 0.95 - 1.05. With regard to the measurement of the randomness index, it can be performed via H- NMR.
  • C 6 (adipic acid), C 7 (pimelic acid), Cs (suberic acid), C 9 (azelaic acid), Cio (sebacic acid), Cn (undecandioic acid), C 12 (dodecandioic acid) and C 13 (brassylic acid) are preferred.
  • particularly preferred are aliphatic diacids from renewable sources and preferably Cs (suberic acid), C 9 (azelaic acid), C 10 (sebacic acid), C 12 (dodecandioic acid) and C 13 (brassylic acid) and their esters.
  • Even more preferred are aliphatic acids from renewable sources C 9 (azelaic acid), C 10 (sebacic acid) and their esters. Mixtures of these acids are also particularly interesting.
  • Polyfunctional aromatic acids are intended as dicarboxylic aromatic compounds of the phthalic acid type and their esters and dicarboxylic aromatic compounds of renewable origin and their esters. Particularly preferred are 2,5 furandicarboxylic acid and its esters and terephthalic acid and its esters, and mixtures thereof.
  • diols in accordance with the present invention are 1 ,2-ethanediol, 1 ,2- propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7- heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 , 10-decanediol, 1 , 1 1-undecanediol, 1 , 12- dodecanediol, 1 , 13-tridecanediol, 1 ,4-cyclohexanedimethanol, propylene glycol, neo-pentyl glycol, 2-methyl- 1 ,3-propanediol, dianhydro sorbitol, dianhydromannitol,
  • the content of aromatic polyfunctional acids is preferably comprised between 30-80%, more preferably between 40- 70% and even more preferably between 46-60% by moles with respect to the total molar content of dicarboxylic acids.
  • the precursor polyester PP can contain, in addition to the base monomers, at least one hydroxy acid or their lactide or lactone, in a quantity comprised between 0-49%, preferably between 0-30% by moles with respect to the molar content of repeating units.
  • Suitable hydroxy acids are glycolic, hydroxybutyric, hydroxycaproic, hydroxyvaleric, 7- hydroxy heptanoic, 8-hydroxycaproic, 9-hydroxynonanoic acid, lactic acid or lactide.
  • the hydroxy acids can be inserted in the chain as is or can also be previously made to react with diacids or diols.
  • Long bifunctional molecules can also be added in quantities not exceeding 10%>, also with functionality not in terminal position.
  • Examples are dimer acids, ricinoleic acid and acids having epoxy functionalities.
  • Amines, amino acids and amino alcohols can also be present in percentages of up to 30% by moles with respect to all the other components.
  • one or more polyfunctional molecules i.e. molecules having more than 2 reactively active sites
  • one or more polyfunctional molecules in quantities of between 0.02 and 3% by moles with respect to the quantity of dicarboxyl acids (and hydroxy acids if present), can advantageously be added in order to obtain branched products.
  • Examples of these molecules are glycerol, pentaerythritol, trimethylol propane, citric acid, dipentaerythritol, monoanhydrosorbitol, monohydro-mannitol, acid triglycerides and triethanolamine.
  • the precursor polyester PP is characterized in melted state by a Melt Flow Rate comprised between 300 and 2, more preferably between 100 and 5 g/10 min (measurement taken at 190°C/2.16 kg according to the standard ASTM D1238-89) and by a content of caboxyl end groups of less than 150, more preferably less than 50 and even more preferably less than 35 meq KOH/kg of polymer.
  • a Melt Flow Rate comprised between 300 and 2, more preferably between 100 and 5 g/10 min (measurement taken at 190°C/2.16 kg according to the standard ASTM D1238-89) and by a content of caboxyl end groups of less than 150, more preferably less than 50 and even more preferably less than 35 meq KOH/kg of polymer.
  • the measurement of the content of carboxyl end groups can be carried out as follows: 1.5-3 g of polyester are placed in a 100 ml Erlenmeyer flask together with 60 ml of chloroform. After complete dissolution of the polyester, 25 ml of 2-propanol and, immediately before analysis, 1 ml of deionised water are added. The solution thus obtained is titrated with a preliminary standardized KOH/ethanol solution. A suitable indicator is used to determine the equivalence point of the titration, such as a glass electrode for acid-base titrations in non-aqueous solvents.
  • the carboxyl end group content is calculated from consumption of the KOH/ ethanol solution according to the following equation:
  • T concentration of the KOH/ethanol solution expressed in moles/liter
  • the precursor polyester PP can also be used in blends both with other precursor polyesters of the same type and/or with other polymers both of natural or synthetic origin carrying an unsaturated terminal group.
  • particularly preferred are carbohydrates, polyesters such as polyhydroxyalkanoates, polylactides, polylactones; polyester-urethanes, polyurethanes, polyamides, polycarbonates, polyolefms.
  • the production process of the precursor polyester PP can take place according to any of the processes known to the state of the art.
  • the polyesters can advantageously be obtained with a polycondensation reaction.
  • the unsaturated terminator can be added either during the polycondensation step or during a step subsequent thereto.
  • the polymerization process of the precursor polyester PP can be conducted in the presence of a suitable catalyst.
  • a suitable catalyst metallo -organic compounds of tin, for example derivatives of stannoic acid, titanium compounds, for example orthobutyl titanate, and aluminium compounds, for example Al-triisopropyl, antimony compounds and zinc compounds may, for example, be used.
  • the present invention also relates to the process for the preparation of the substantially gel- free and substantially linear biodegradable polyester BP comprising units deriving from at least one diacid and at least one diol, said process consisting of mixing and reacting with a radical initiator a precursor polyester provided with an unsaturated chain terminator, said terminator having formula:
  • T is selected from the group consisting of hydroxylic, carboxylic, amine, amide or ester group, and "n" is an integer number comprised between 0 and 13.
  • One or more radical initiators such as peroxides can be use for said process.
  • organic peroxides such as diacyl peroxides, peroxy esters, dialkyl peroxides, hydroperoxides, peroxy ketals and carbonate peroxides.
  • Diacyl peroxides and dialkyl peroxides are preferred.
  • peroxides examples include benzoyl peroxide, lauroyl peroxide, isononanoyl peroxide, dicumyl peroxide, di-(tert-butylperoxyisopropyl) benzene, alpha,alpha'di-(tert-butylperoxy) diisopropylbenzene, tert-butylperoxide, 2,5dimethyl-2-5- di(tertbutyl) peroxy hexane and mixtures thereof.
  • Said organic peroxides are advantageously added in quantities less than 0.08% by weight, preferably less than 0.05%, more preferably below 0.03% and still more preferably below 0.02% with respect to the quantity of polyester (and other polymers in the case of blend).
  • the skilled person will easily be able to identify the effective quantity of peroxide required in relation to the properties desired for the polymer.
  • Said peroxides can be advantageously added as masterbatches in order to facilitate their mixing with the polyester precursor.
  • Said process is preferably conducted by reactive extrusion.
  • the biodegradable polyester BP can have terminal double bonds and/or adducts deriving from the reaction of the chain terminator with the radical initiators.
  • the presence of the terminal double bonds and/or adducts deriving from the reaction of the chain terminator with the radical initiators can be determined with different methods well known to those skilled in the art, such as NMR spectroscopy or by methano lysis reactions of the polymer chain coupled with chromatographic methods combined with mass spectrometry.
  • NMR spectroscopy or by methano lysis reactions of the polymer chain coupled with chromatographic methods combined with mass spectrometry.
  • the skilled person will easily be able to identify structures referable either to the unsaturated chain terminator or to the reacted chain terminator after the reaction of its terminal double bond.
  • the biodegradable polyester BP is biodegradable according to the standard EN 13432.
  • the biodegradable polyester BP according to the invention can also be used in blends, also obtained by reactive extrusion, both with polyesters of the same type and with other biodegradable polyesters (such as poly L lactic acid, poly D lactic acid and stereocomplex poly D-L lactic acid, poly-8-caprolactone, polyhydroxybutyrates, such as hydroxybutyrate- valerate, polyhydroxybutyrate-propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate- hexadecanoate, polyhydroxybutyrate-octadecanoate, polyalkylene succinates), poly-3- hydroxybutyrate, poly-4-hydroxybutyrate, polysuccinates and in particular polyalkylene succinate and its copolymers with adipic acid and lactic acid or other polymers different from polyesters where the alkylene can be butylene, propylene,
  • the biodegradable polyester BP according to the invention can also be used in blends with polymers of natural origin, such as starch, cellulose, chitin, chitosan, alginates, proteins such as gluten, zein, casein, collagen, gelatin, natural rubbers, rosin acid and its derivatives, lignins and their derivatives.
  • the starches and celluloses can be modified, and among these starch or cellulose esters with substitution degree between 0.2 and 2.5, hydroxypropylated starches and modified starches with fatty chains may, for example, be mentioned.
  • the starch can also be used both in destructured and gelatinized form or as a filler.
  • the starch can represent the continuous or dispersed phase or can be in co-continuous form. In the case of dispersed starch, the starch is preferably in a form of less than 1 micron and more preferable less than 0.5 ⁇ of average diameter.
  • the biodegradable polyester BP of the invention can also be blended with polyolefms such as polyethylene, polypropylene, their copolymers, polyvinyl alcohol, polyvinyl acetate, polyethylene vinyl acetate and polyethylene vinyl alcohol, urethane polyesters, polyurethanes, polyamides, polyureas, PET, PBT, PTT and polycarbonates such as polyalkylenecarbonates.
  • polyolefms such as polyethylene, polypropylene, their copolymers, polyvinyl alcohol, polyvinyl acetate, polyethylene vinyl acetate and polyethylene vinyl alcohol, urethane polyesters, polyurethanes, polyamides, polyureas, PET, PBT, PTT and polycarbonates such as polyalkylenecarbonates.
  • the biodegradable polyester BP and the precursor polyester PP according to the present invention can also be used as prepolymers to produce polyurethanes and polyureas.
  • the precursor polyester PP can also be advantageously made to react with precursor polymers of the same type or of different type to produce block copolymers, compatibilizers of different types, tie layers, starch complexation agents, hydrophobic-hydrophilic structures etc., so as to obtain products capable of avoiding or limiting to a minimum the use of additives with high environmental impact.
  • mixtures of biodegradable polyester BP according to the invention with starch are particularly preferred.
  • the films obtained with said mixtures have high mechanical properties which, advantageously can reach tear strength values higher than 100 N/mm at room temperature and 50%RH..
  • biodegradable polyester BP according to the invention can also be used in blends with polymers of synthetic origin and with the polymers of natural origin mentioned above. Mixtures of the biodegradable polyester BP with starch and polylactic acid or polyhydroxyalkanoates are particularly preferred.
  • the biodegradable polyester BP according to the invention has properties that make it suitable for use, by appropriately modulating the relative molecular weight, in numerous practical applications, such as films, injection molded products, extrusion coating products, fibers, foams, thermo formed products, etc..
  • biodegradable polyesters BP according to the invention are suitable for producing: - mono- and bi-oriented films, and films multilayered with other polymeric materials;
  • films for use in the agricultural sector such as films for use in mulching
  • thermo formed foodstuff packaging both mono- and mult i- layered, as in containers for milk, yogurt, meats, beverages, etc.;
  • thermoformed foam sheets thermoformed foam sheets, and containers obtained from them for use in foodstuff packaging;
  • the core is constituted by rigid polymers such as PLA, PET, PTT etc.
  • the shell is constituted by the material of the invention, composite fibres from blends, fibres with different sections, from circular to multilobed, staple fibres, woven and nonwoven fabrics or spun bonded or thermobonded for use in sanitary and hygiene products, and in the agricultural and clothing sectors;
  • biodegradable polyester according to the present invention odorless, it is particularly suitable for the production of films and bags for packaging, preferably for food packaging.
  • the biodegradable polyester BP according to the invention can also be used as component of multilayer films wherein the different types of BP are used for the different layers also in combination with layers of cellophane, destructured starch, PLA or other polymers having high barrier properties to oxygen and/or fats.
  • the biodegradable polyester BP is characterised for being odourless and for a high degree of transparency, which make it advantageous for use in the food sector.
  • a 25 1 reactor provided with a mechanical stirrer, an inlet for nitrogen flow, a condenser and a connection to a vacuum pump, was loaded with the following:
  • omega-undecenoic acid 8.43 g (0.046 moles)
  • the temperature was gradually increased under vigorous stirring and nitrogen flow to 210°C.
  • the reaction was continued until 90% of the theoretical quantity of light by-products was distilled.
  • the temperature was then increased to 240 °C and the system was subjected to a pressure of 0.6 mmHg. The reaction was continued for 120 min.
  • a biodegradable polyester PB having the following properties is obtained:
  • the polyester is odorless.
  • Thermo Trace-DSQ II gas chromatograph provided with split/splitless injector used in splitless configuration (injector temperature 300°C) and a Trace TR-5MS capillary column (length 15 m, diameter 0.25 mm, stationary phase 95% dimethyl-/ 5% diphenyl- polysiloxane and stationary phase thickness 0.25 ⁇ ).
  • the carrier gas used for analysis is He (flow 1.2 ml/min).
  • the elution program consists in a temperature ramp that starts from 100°C up to 300°C with a gradient of 15°C/min.
  • the injected volume is of 1 microliter.
  • the mass detector is provided with electronic impact ionization set at 220°C with positive ionization and was set in Total Ion Current mode between 40 and 600 m/z.
  • Figure 1-a shows the gas chromatographic trace obtained by analyzing the sample of biodegradable polyester according to Example 1.
  • the gas chromatographic trace shows one chromatographic peak, with retention time of 3.52 minutes, which can be used for the identification of the biodegradable polyester according to Example 1.
  • Figure 1-b shows the gas chromatographic trace obtained by analyzing a sample of a poly(butylene terephthalate-co-butylene sebacate) at 56% by moles of aromatic units without unsaturated chain terminator which was previously subjected to reactive extrusion with 0.012% in weight of alpha'-di(t-butyl peroxy) diisopropylbenzene.
  • the gas chromatographic trace shows no peak at or around the retention time of 3.52 minutes.
  • Figure 2-a shows the detail of the mass spectrum of the peak at 3.52 minutes of the gas chromatographic trace shown in Figure 1-a. Said peak is referable to the reacted unsaturated chain terminator of Example 1 after the reaction of its terminal double bond.
  • Figure 2-b shows a detail of the gas chromatographic trace of Figure 1-b corresponding to a retention time of 3.52 minutes.
  • Figures 2-b has no peak corresponding to the chromatographic peak of the polyester according to Example 1.
  • Starch based Blend 63 parts in weight of the biodegradable polyester BP obtained in Example 1 were mixed with 5 parts of poly-L-lactic acid (Mn of 130 000, MFR at 190°C, 2.16 kg of 3.5 g/10 min, lactide residue of less than 0.2% and D-isomer content of around 6%>), 23.4 parts starch, 3.5 parts water and 5 parts glycerol in a Haake Rheocord 90 Rheomex TW-100 twin screw extruder.
  • the thermal profile was maintained between 120 and 190°C.
  • the final water content of the granule was equal to 0.8%>.
  • the film obtained was subjected to mechanical characterization tests. Each parameter was determined by means of at least 6 replicates on randomly obtained specimen of films. The values herewith reported correspond to the arithmetic mean of these replicas.
  • a 25 1 reactor provided with a mechanical stirrer, an inlet for nitrogen flow, a condenser and a connection to a vacuum pump, was loaded with the following:
  • omega-undecenoic acid 67.45 g ( 0.366 moles)
  • the temperature was gradually increased under vigorous stirring and nitrogen flow to 210°C.
  • the reaction was continued until 90% of the theoretical quantity of light by-products was distilled.
  • the temperature was then increased to 240 °C and the system was subjected to a pressure of 0.6 mmHg. The reaction was continued for 120 min.
  • a 25 1 reactor provided with a mechanical stirrer, an inlet for nitrogen flow, a condenser and a connection to a vacuum pump, was loaded with the following:
  • omega-undecenoic acid 112.4 g (0.61 moles)
  • the temperature was gradually increased under vigorous stirring and nitrogen flow to 210°C.
  • the reaction was continued until 90% of the theoretical quantity of light by-products was distilled.
  • the temperature was then increased to 240 °C and the system was subjected to a pressure of 0.6 mmHg. The reaction was continued for 120 min.
  • a biodegradable polyester PB having the following properties is obtained:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Materials For Medical Uses (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne un polyester biodégradable sensiblement dépourvu de gel et sensiblement linéaire qui peut être obtenu par le biais d'une réaction avec des initiateurs radicalaires démarrant à partir d'un polyester précurseur à terminateur de chaîne insaturée. Ce terminateur est de formule T-(CH2)n-CH=CH2, dans laquelle "T" peut être un groupe hydroxylique carboxylique, amine, amide ou ester, et "n" est un entier compris entre 0 et 13.
PCT/EP2010/064185 2009-09-25 2010-09-24 Polyester biodégradable WO2011036272A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201080042753.9A CN102666619B (zh) 2009-09-25 2010-09-24 可生物降解的聚酯
CA2773445A CA2773445C (fr) 2009-09-25 2010-09-24 Polyester biodegradable
EP10766247.0A EP2480582B1 (fr) 2009-09-25 2010-09-24 Polyester biodégradable
JP2012530280A JP5793497B2 (ja) 2009-09-25 2010-09-24 生分解ポリエステル
ES10766247T ES2788006T3 (es) 2009-09-25 2010-09-24 Poliéster biodegradable
US13/497,864 US10017597B2 (en) 2009-09-25 2010-09-24 Biodegradable polyester

Applications Claiming Priority (2)

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ITMI2009A001641 2009-09-25
ITMI2009A001641A IT1395925B1 (it) 2009-09-25 2009-09-25 Poliestere biodegradabile.

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WO2011036272A2 true WO2011036272A2 (fr) 2011-03-31
WO2011036272A3 WO2011036272A3 (fr) 2011-06-09

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JP (1) JP5793497B2 (fr)
CN (1) CN102666619B (fr)
CA (1) CA2773445C (fr)
ES (1) ES2788006T3 (fr)
IT (1) IT1395925B1 (fr)
WO (1) WO2011036272A2 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2746525B2 (ja) 1993-09-22 1998-05-06 昭和高分子株式会社 生分解性高分子量ポリエステルの製造方法
WO2006053936A1 (fr) 2004-11-17 2006-05-26 Jvs-Polymers Oy Biopolymere reticulable

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2600474B2 (ja) 1990-05-08 1997-04-16 日立化成工業株式会社 共重合体の製造法
JP2003221423A (ja) * 2002-02-01 2003-08-05 Aeba Toshiyuki 複合樹脂組成物とその製造方法
ITMI20020865A1 (it) * 2002-04-22 2003-10-22 Novamont Spa Poliesteri biodegradabili ottenuti mediante estrusione reattiva
KR101080735B1 (ko) * 2004-03-04 2011-11-07 유니티카 가부시끼가이샤 생분해성 폴리에스테르 수지 조성물, 그 제조방법, 및그들로부터 얻어지는 발포체 및 성형체
ITMI20050452A1 (it) * 2005-03-18 2006-09-19 Novamont Spa Poliestere biodegradabile alifatico-aromatico
EP2004703B1 (fr) * 2006-04-19 2010-11-24 Stepan Company Formules durcissables par rayonnements pour résistance au vieillissement améliorée

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2746525B2 (ja) 1993-09-22 1998-05-06 昭和高分子株式会社 生分解性高分子量ポリエステルの製造方法
WO2006053936A1 (fr) 2004-11-17 2006-05-26 Jvs-Polymers Oy Biopolymere reticulable

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Publication number Publication date
IT1395925B1 (it) 2012-11-02
EP2480582A2 (fr) 2012-08-01
CA2773445C (fr) 2018-07-10
ITMI20091641A1 (it) 2011-03-26
WO2011036272A3 (fr) 2011-06-09
EP2480582B1 (fr) 2020-04-08
US20120178896A1 (en) 2012-07-12
CN102666619A (zh) 2012-09-12
JP2013506024A (ja) 2013-02-21
JP5793497B2 (ja) 2015-10-14
ES2788006T3 (es) 2020-10-20
US10017597B2 (en) 2018-07-10
CN102666619B (zh) 2015-11-25
CA2773445A1 (fr) 2011-03-31

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